Process for producing carbonyl or hydroxy compound

ABSTRACT

There are disclosed are a method for producing at least one compound selected from a carbonyl compound and a hydroxy adduct compound by an oxidative cleavage or addition reaction of an olefinic double bond of an olefin compound,  
     which contains  
     reacting an olefin compound with hydrogen peroxide, utilizing as a catalyst, at least one member selected from  
     (a) tungsten,  
     (b) molybdenum, or  
     (c) a tungsten or molybdenum metal compound containing  
     (ia) tungsten or (ib) molybdenum and  
     (ii) an element of Group IIIb, IVb, Vb or VIb excluding oxygen, and  
     a catalyst composition.

BACKGROUND OF THE INVENTION FIELD OF THE INVENTION

[0001] The present invention relates to an oxidation catalyst andmethods using the same for producing carbonyl compounds and hydroxyadduct compounds by oxidative cleavage of an olefinic double bond oraddition reaction thereto.

[0002] A method for producing adipic acid by reacting, in the presenceof sodium tungstate and trioctylmethylammonium sulfate, cyclohexene withan aqueous hydrogen peroxide is known (JP-A 2000-86574), and a methodfor producing an aldehyde by reacting an olefin with hydrogen peroxide,using heteropolyacid containing phosphorus or germanium, is also known(JP-B 6-84324).

[0003] However, yields of the desired products in these methods were notalways satisfactory for an industrial scale of production.

SUMMARY OF THE INVENTION

[0004] According to the present invention, carbonyl compounds andhydroxy adduct compounds can be obtained by using a readily availableoxidation catalyst, which can selectively provide desired compounds inan improved yield.

[0005] Thus, the present invention provides:

[0006] 1. a method for producing at least one compound selected from acarbonyl compound and a hydroxy adduct compound by an oxidative cleavageor addition reaction of an olefinic double bond of an olefin compound,

[0007] which comprises

[0008] reacting an olefin compound with hydrogen peroxide, utilizing asa catalyst, at least one member selected from

[0009] (a) tungsten,

[0010] (b) molybdenum or

[0011] (c) a tungsten or molybdenum metal compound comprising

[0012] (ia) tungsten or (ib) molybdenum and

[0013] (ii) an element of Group IIIb, IVb, Vb or VIb excluding oxygen;

[0014] 2. an oxidation catalyst composition obtained by reacting aqueoushydrogen peroxide with at least one member selected from

[0015] a tungsten or molybdenum metal compound comprising

[0016] (ia) tungsten or (ib) molybdenum, and

[0017] (ii) an element of Group IIIb, IVb, Vb or VIb excluding oxygen,provided that said tungsten metal compound is not tungsten carbide;

[0018] 3. an oxidation catalyst composition

[0019] obtained by

[0020] reacting aqueous hydrogen peroxide with at least one memberselected from

[0021] (a) tungsten,

[0022] (b) molybdenum, or

[0023] (c) a tungsten or molybdenum metal compound comprising

[0024] (ia) tungsten or (ib) molybdenum, and

[0025] (ii) an element of Group IIIb, IVb, Vb or VIb excluding oxygen,and containing an organic solvent;

[0026] 4. a method for producing a carbonyl compound of formula (II):

R_(a)R_(b)C═O   (II)

[0027] wherein a and b respectively represent 1 and 2, or 3 and 4, whichcomprises subjecting a hydroxy adduct compound of formula (III):

X—(R₁)(R₂)C—C(R₃)(R₄)OH   (IIIa)

[0028] wherein X is a hydroperoxide group, and R₁ to R₄ represent ahydrogen atom or an organic residue, to a decomposition reaction;

[0029] 5. a method for producing a hydroxy adduct compound of formula(IIIb):

X—(R₁)(R₂)C—C(R₃)(R₄)OH   (IIIb)

[0030] wherein X is a hydroxy group and R₁ to R₄ independently representa hydrogen atom or an organic residue, which comprises reacting ahydroxy adduct compound of formula (IIIa):

X—(R₁)(R₂)C—C(R₃)(R₄)OH   (IIIa)

[0031] wherein X is a hydroperoxide group, and R₁ to R₄ are the same asdefined above, with a reducing agent;

[0032] 6. a hydroxy adduct compound of formula (III):

X—(R₁)(R₂)C—C(R₃)(R₄)OH   (III)

[0033] wherein X is a hyroperoxide group or a hydroxy group, R₁ and R₂represent a methyl group, R₃ represents a hydrogen atom, and R₄represents a group of formula:

[0034] wherein R′ is an alkyl, aryl or aralkyl group; and

[0035] 7. a hydroxy adduct compound of formula (IIIa):

X—(R₁)(R₂)C—C(R₃)(R₄)OH   (IIIa)

[0036] wherein X represents a hyroperoxide group, R₁ represents a methylgroup, R₃ represents a hydrogen atom, and R₂ and R₄ form a group offormula:

DETAILED DESCRIPTION OF THE INVENTION

[0037] First, the method for producing at least one compound selectedfrom a carbonyl compound and a hydroxy adduct compound by an oxidativecleavage or addition reaction of an olefinic double bond of an olefincompound is described.

[0038] The method is conducted, for example, by reacting the olefincompound and the metal or the metal compound, which is utilized as acatalyst, with hydrogen peroxide, or it may be conducted in such amanner that the metal or the metal compound is reacted with aqueoushydrogen peroxide to form a catalyst composition and subsequently theolefin compound is reacted with hydrogen peroxide in the presence of thecatalyst composition so produced. Thus the production method may beconducted by reacting hydrogen peroxide with the metal or the metalcompound, and reacting the olefin compound with hydrogen peroxide,simultaneously in the same reactor, or in the presence of the catalystcomposition.

[0039] The metal or the metal compound is described below.

[0040] Examples of the tungsten metal compound comprising tungsten andan element of Group IIIb include tungsten boride and the like. Examplesof the tungsten metal compound comprising tungsten and an element ofGroup IVb include tungsten carbide, tungsten silicide and the like.Examples of the tungsten metal compound comprising tungsten and anelement of Group Vb include tungsten nitride, tungsten phosphide.Examples of the tungsten metal compound comprising tungsten and anelement of Group VIb other than oxygen include tungsten sulfide and thelike. Preferred are tungsten, tungsten boride, tungsten carbide andtungsten sulfide.

[0041] Example of the molybdenum metal compound comprising molybdenumand an element of Group IIIb include molybdenum boride, Examples of themolybdenum metal compound comprising molybdenum and an element of GroupIVb include molybdenum carbide, molybdenum silicide and the like.Examples of the molybdenum metal compound comprising molybdenum and anelement of Group Vb include molybdenum nitride, molybdenum phosphide andthe like. Examples of the molybdenum metal compound comprisingmolybdenum and an element of Group VIb other than oxygen includemolybdenum sulfide and the like. Preferred are molybdenum and molybdenumboride.

[0042] Any shape of the metal compounds can be used in the presentinvention. Preferred are those of smaller particle. A catalytic amountof the metal or metal compound may be used in the present productionmethod. A typical amount thereof may be 0.001 to 0.95 mole per mol ofthe olefin compound.

[0043] Hydrogen peroxide is usually used in a form of an aqueoussolution. A solution of hydrogen peroxide in an organic solvent may alsobe used. Any concentration of hydrogen peroxide in an aqueous solutionor in an organic solvent solution may be used, and preferredconcentration is 1 to 60% by weight. For example, commercially availableaqueous hydrogen peroxide may be used without any modification, or, ifnecessary, it may be used after adjustment of its concentration bydilution, concentration or the like.

[0044] The solution of hydrogen peroxide in an organic solvent can beprepared, for example, by such means as extracting of an aqueoushydrogen peroxide solution with an organic solvent or removing water bydistillation of the aqueous solution, preferably in the presence of anappropriate organic solvent, which includes such a solvent that may forman azeotrope with water. Examples of the organic solvent include ethertype solvents such as diethyl ether, methyl tert-butyl ether,tetrahydrofuran or the like, ester solvents such as ethyl acetate or thelike, alcohol solvents such as methanol, ethanol, tert-butanol or thelike, and alkylnitrile solvents such as acetonitrile, propionitrile orthe like. Any amount of organic solvents may be used, and is typicallynot more than 100 parts by weight per 1 part by weight of the olefincompound. Preferred organic solvent is an inert organic solvent and isfor example, t-butanol or methyl t-butyl ether.

[0045] The amount of hydrogen peroxide that may be used is usually notless than 1 mole per mol of the olefin compound. There is no particularupper limit of the amount of hydrogen peroxide that may be used, but apreferred amount thereof is not more than 50 moles per mol of the olefincompound, and a preferred amount thereof may be set for the olefincompound and the desired products therefrom as below.

[0046] The oxidation catalyst composition of the present productionmethod can be obtained by reacting aqueous hydrogen peroxide with atleast one metal or metal compound as described above to form thecatalyst composition as a homogeneous solution or a suspension, both ofwhich can be used. The amount of the hydrogen peroxide is preferably 5moles or more per mol of the metal or the metal compound. The organicsolvent as described above may be used to produce the catalystcomposition containing the organic solvent, which may be furtherdehydrated prior to use, if necessary. Typical examples of thedehydrating agents include anhydrous magnesium sulfate, anhydrous sodiumsulfate, anhydrous boric acid, polyphosphoric acid, diphosphorouspentaoxide and the like.

[0047] The reacting of the metal or the metal compound with hydrogenperoxide may be conducted at any temperature, and preferably at −10 to100° C.

[0048] In the present production method, the carbonyl compound and thehydroxy adduct compound can be obtained by an oxidative cleavage andaddition reaction of an olefinic double bond of an olefin compound.

[0049] The carbonyl compound, which results in the oxidative cleavage ofthe olefin double bond, optionally followed by further oxidation,include ketone, aldehyde, and a carboxylic acid, and the hydroxy adductcompound include diol or β-hydroxyhydroperoxide compound.

[0050] The olefin compound that may be used include an olefin compoundof formula (I):

R₁R₂C═CR₃R₄   (I),

[0051] wherein R₁ to R₄ are the same or different and represent ahydrogen atom or an organic residue, and two geminal groups or twogroups which are in syn position among the R₁, R₂, R₃ and R₄ groups mayform a divalent organic residue, provided that R₁ to R₄ do notsimultaneously represent a hydrogen atom.

[0052] The carbonyl compound that may be produced includes a carbonylcompound of formula (II):

R_(a)R_(b)C═O   (II),

[0053] wherein a and b respectively represent 1 and 2, or 3 and 4, orR_(b) represents a hydroxy group.

[0054] The carbonyl compound of formula (II) above include a compound offormula (IV):

R₁R₂C═O, and R₃R₄C═O   (IV)

[0055] wherein R₁ to R₄ are the same as defined above.

[0056] The hydroxy adduct compound that may be produced include acompound of formula (III):

X—(R₁)(R₂)C—C(R₃)(R₄)OH   (III)

[0057] wherein X represents a hydroxy group or a hydroperoxide group.

[0058] Substituent groups R₁ to R₄ are described below.

[0059] Examples of the organic residue include alkyl, alkoxy, aryl,aryloxy, aralkyl and aralkyloxy groups, alkylcarbonyl, arylcarbonyl,aralkylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, aralkyloxycarbonyl,carboxyl and carbonyl groups, all of which may be substituted.

[0060] The divalent organic residue means a group formed by the abovedescribed groups and specific examples thereof include an alkylene,oxaalkylene, arylene, oxaarylene, aralkylene, oxaaralkylene,alkylenecarbonyl, arylenecarbonyl, aralkylenecarbonyl,alkyleneoxacarbonyl, arylenoxacarbonyl, aralkylenoxacarbonyl groups orthe like, all of which may be substituted.

[0061] Preferred organic residue are alkyl, aryl, aralkyl,alkylcarbonyl, arylcarbonyl, aralkylcarbonyl, alkoxycarbonyl,aryloxycarbonyl, aralkyloxycarbonyl, carboxyl and carbonyl groups, allof which may be substituted and corresponding divalent organic residues,which may be substituted.

[0062] The alkyl groups in the alkyl, alkoxy, aralkyl, aralkyloxy,alkylcarbonyl, aralkylcarbonyl, alkoxycarbonyl and aralkyloxycarbonylgroups include a linear, branched or cyclic alkyl group having 1 to 20carbon atoms such as a methyl group, an ethyl group, a n-propyl group,an isopropyl group, a n-butyl group, an isobutyl group, a sec-butylgroup, a tert-butyl group, a n-pentyl group, a n-hexyl group, a n-heptylgroup, a n-octyl group, a n-nonyl group, a n-decyl group, a cyclopropylgroup, a 2,2-dimethylcyclopropyl group, a cyclopentyl group, acyclohexyl group and a menthyl group.

[0063] Examples of the aryl groups in the aryl, aryloxy, aralkyl,aralkyloxy, arylcarbonyl, aralkylcarbonyl, aryloxycarbonyl andaralkyloxycarbonyl groups include a phenyl group, a naphthyl group andthe like.

[0064] The aralkyl group means a group comprising the ary group and thealkyl group as described above.

[0065] The alkoxy, aryoxy and aralkyloxy groups mean groups thatrespectively comprising corresponding alkyl, aryl and aralkyl groups andan oxy group.

[0066] The alkylcarbonyl, arylcarbonyl, aralkylcarbony, alkoxycarbonyl,aryoxycarbonyl, aralkyloxycarbony groups mean groups respectivelycomprising alkyl, aryl, aralkyl, alkoxy, aryoxy and aralkyloxy groupsand a carbonyl group.

[0067] Examples of the alkyl groups, which may be substituted, forexample, include an alkyl group substituted with the alkoxy, aryloxy oraralkyloxy group, the halogen atom, the alkylcarbonyl, arylcarbonyl,alkoxycarbonyl, aryloxycarbonyl, aralkyloxycarbonyl, carboxyl orcarbonyl group as described above.

[0068] The alkyl moieties of the alkoxy, alkoxycarbonyl, alkylcarbonylmay also be substituted as the alkyl groups described above.

[0069] Examples of the halogen atoms include a fluorine atom, a chlorineatom, a bromine atom and the like.

[0070] Specific examples of the alkyl groups, which may be substitutedinclude, for example, a chloromethyl group, a fluoromethyl group, atrifluoromethyl group, a methoxymethyl group, an ethoxymethyl group, amethoxyethyl group, a carbomethoxymethyl group and the like.

[0071] The aryl groups in the aryl, aryloxy, aralkyl, aralkyloxy,arylcarbonyl, aralkylcarbonyl, aryloxycarbonyl and aralkyloxycarbonylgroups may be substituted with the alkyl, aryl, alkoxy, aralkyl, aryloxyor aralkyloxy group or a halogen atom as described above.

[0072] Specific examples of the aryl groups, which may be substitutedinclude, for example, a phenyl group, a naphthyl group, a 2-methylphenylgroup, a 4-chlorophenyl group, a 4-methylphenyl group, 4-methoxyphenylgroup, a 3-phenoxyphenyl group and the like.

[0073] Specific examples of the aryloxy group, which may be substitutedinclude, for example, a phenoxy group, a 2-methylphenoxy group, a4-chlorophenoxy group, a 4-methylphenoxy group, a 4-methoxyphenoxy groupand a 3-phenoxyphenoxy group.

[0074] Specific examples of the aralkyl group, which may be substitutedinclude, for example, a benzyl group, a 4-chlorobenzyl group, a4-methylbenzyl group, a 4-methoxybenzyl group, a 3-phenoxybenzyl group,a 2,3,5,6-tetrafluorobenzyl group, a 2,3,5,6-tetrafluoro-4-methylbenzylgroup, a 2,3,5,6-tetrafluoro-4-methoxybenzyl group, a2,3,5,6-tetrafluoro-4-methoxymethylbenzyl group and the like.

[0075] Examples of the alkylcarbonyl, arylcarbonyl, and aralkylcarbonylgroups respectively include, for example, a methylcarbonyl group, anethylcarbonyl group, a phenylcarbonyl group, a benzylcarbonyl group andthe like.

[0076] Examples of the alkoxycarbonyl, aryloxycarbonyl andaralkyloxycarbonyl groups respectively include, for example, amethoxycarbonyl group, an ethoxycarbonyl group, a phenoxycarbonyl group,a benzyloxycarbonyl group and the like.

[0077] Specific examples of the linear, branched or cyclic alkoxy groupshaving 1 to 20 carbon atoms include a methoxy group, an ethoxy group, an-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxygroup, a sec-butoxy group, a tert-butoxy group, a n-pentyloxy group, an-decyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, amenthyloxy group and the like.

[0078] Examples of the alkoxy group, which may be substituted include,for example, a chloromethoxy group, a fluoromethoxy group, atrifluoromethoxy group, a methoxymethoxy group, an ethoxymethoxy group,a methoxyethoxyl group and the like.

[0079] Specific examples of the aralkyloxy group, which may besubstituted include a benzyloxy group, a 4-chlorobenzyloxy group, a4-methylbenzyloxy group, a 4-methoxybenzyloxy group, a3-phenoxybenzyloxy group, a 2,3,5,6-tetrafluorobenzyloxy group, a2,3,5,6-tetrafluoro-4-methylbenzyloxy group, a2,3,5,6-tetrafluoro-4-methoxybenzyloxy group, a2,3,5,6-tetrafluoro-4-methoxymethylbenzyloxy group and the like.

[0080] Examples of the olefin of formula (I) wherein three of the R₁ toR₄ groups represent a hydrogen atom, which are referred to as“mono-substituted olefin” include 1-hexene, 1-heptene, 1-octene,1-undecene, styrene, 1,7-octadiene and allyl benzyl ether. Furtherexamples of the olefin compound, which are referred to as“di-substituted terminal olefin”, include 2-methylpropene,2-methyl-4,4-dimethyl-1-propene, 2-ethyl-1-butene, 2-methyl-1-pentene,α-methylstyrene, α-phenylstyrene, methylenecyclobutane,methylenecyclopentane, methylenecyclohexane, β-pinene, camphene,1,3,3-trimethyl-2-methylindorine and α-methylene-γ-butyrolactone.

[0081] Examples of the olefin of formula (I) wherein two groups of R₁ toR₄ groups represent a hydrogen atom, which are referred to as“di-substituted internal olefin, include cyclopentene, cyclohexene,cycloheptene, cyclooctene, 3-methylcyclopentene, 4-methylcyclopentene,3,4-dimethylcyclopentene, 3,5-dimethylcyclopentene,3,4,5-trimethylcyclopentene, 3-chlorocyclopentene, 3-methylcyclohexene,4-methylcyclohexene, 3,4-dimethylcyclohexene, 3,5-dimethylcyclohexene,3,4,5-trimethylcyclohexene, 2-hexene, 3-hexene, 5-dodecene, norbornene,phenanthrene, 1,2,3,4-tetrahydrophthalic anhydride, dicyclopentadiene,indene, methyl 3,3-dimethyl-2-(1-propenyl)-cyclopropanecarboxylate,ethyl 3,3-dimethyl-2-(1-propenyl)-cyclopropanecarboxylate and the like.

[0082] Examples of the olefin compound of formula (I) wherein one of theR₁ to R₄ groups represents a hydrogen atom, which are referred to as“tri-substituted olefin”, include 2-methyl-2-pentene,3-methyl-2-pentene, 3-ethyl-2-pentene, 2-methyl-2-hexene,3-methyl-2-hexene, 2-methyl-1-phenylpropene, 2-phenyl-2-butene,1-methylcyclopentene, 1,3-dimethylcyclopentene,1,4-dimethylcyclopentene, 1,5-dimethylcyclopentene,1,3,5-trimethylcyclopentene, 1,3,4-trimethylcyclopentene,1,4,5-trimethylcyclopentene, 1,3,4,5-tetramethylcyclopentene,1-methylcyclohexene, 1,3-dimethylcyclohexene, 1,4-dimethylcyclohexene,1,5-dimethylcyclohexene, 1,3,5-trimethylcyclohexene,1,3,4-trimethylcyclohexene, 1,4,5-trimethylcyclohexene,1,3,4,5-tetramethylcyclohexene, isophorone, 2-carene, 3-carene,α-pinene, methyl3,3-dimethyl-2-(2-methyl-1-propenyl)-cyclopropanecarboxylate, ethyl3,3-dimethyl-2-(2-methyl-1-propenyl)-cyclopropanecarboxylate, isopropyl3,3-dimethyl-2-(2-methyl-1-propenyl)-cyclopropanecarboxylate, tert-butyl3,3-dimethyl-2-(2-methyl-1-propenyl)-cyclopropanecarboxylate, cyclohexyl3,3-dimethyl-2-(2-methyl-1-propenyl)-cyclopropanecarboxylate, menthyl3,3-dimethyl-2-(2-methyl-1-propenyl)-cyclopropanecarboxylate, benzyl3,3-dimethyl-2-(2-methyl-1-propenyl)-cyclopropanecarboxylate,(4-chlorobenzyl)3,3-dimethyl-2-(2-methyl-1-propenyl)-cyclopropanecarboxylate,(2,3,5,6-tetrafluorobenzyl)3,3-dimethyl-2-(2-methyl-1-propenyl)-cyclopropanecarboxylate,(2,3,5,6-tetrafluoro-4-methylbenzyl)3,3-dimethyl-2-(2-methyl-1-propenyl)-cyclopropanecarboxylate,(2,3,5,6-tetrafluoro-4-methoxybenzyl)3,3-dimethyl-2-(2-methyl-1-propenyl)-cyclopropanecarboxylate,(2,3,5,6-tetrafluoro-4-methoxymethylbenzyl)3,3-dimethyl-2-(2-methyl-1-propenyl)-cyclopropanecarboxylate,(3-phenoxybenzyl)3,3-dimethyl-2-(2-methyl-1-propenyl)-cyclopropanecarboxylate and thelike.

[0083] Examples of the olefin compound of formula (I) wherein R₁ to R₄groups do not represent a hydrogen atom, which are referred to as“tetra-substituted olefin”, include 2,3-dimethyl-2-butene,1,2-dimethylcyclopenteen, 1,2-dimethylcyclohexene,1,2,3,4,5,6,7,8-octahydronaphthalene,1-isopropylidene-2-carboethoxy-3-methylcyclopentane,cyclohexylidenecyclohexane, tetraphenylethylene,2,3-dimethyl-4-methoxyindene, 2,3-di(4-acetoxyphenyl)-2-butene, pulegoneand the like.

[0084] The reaction of the olefin compound with hydrogen peroxide istypically conducted at a temperature range of from 0 to 200° C. and thereaction temperature may be preferably set as below within the range inview of the olefin compound and the desired products of the reaction.

[0085] For example, the carbonyl compound of formula (IV) wherein R₁ toR₄ represent an organic residue can be produced, as a major product, byreacting the olefin compound of formula (I) with hydrogen peroxidepreferably in the presence of an organic solvent and a dehydrating agentand at 30 to 100° C., wherein the amount of hydrogen peroxide ispreferably 2 to 10 moles per mol of the olefin compound.

[0086] The carbonyl compound of formula (IV) wherein at least one of R₁to R₄ groups represents a hydrogen atom, can be produced, as a majorproduct, by reacting the olefin compound of formula (I) with hydrogenperoxide preferably in the presence of an organic solvent and adehydrating agent and at 30 to 65° C., wherein the amount of hydrogenperoxide is preferably 2 to 10 moles per mol of the olefin compound.

[0087] The carbonyl compound of formula (II) wherein R_(b) represents ahydroxy group, can be produced, as a major product, by reacting theolefin compound of formula (I) wherein at least one group of R₁ to R₄represents a hydrogen atom, with aqueous hydrogen peroxide preferably at65 to 100° C., wherein the amount of hydrogen peroxide is preferably 4moles or more per mol of the olefin compound.

[0088] The method of the present invention may also be carried out inthe presence of a boron compound such as boric anhydride, Examples ofthe boron compound include boric anhydride, metaboric acid, orthoboricacid, alkali metal salts of metaboric acid, alkaline earth metal saltsof metaboric acid, alkali metal salts of orthoboric acid and alkalineearth metal salts of orthoboric acid. Any amount of such a compound maybe used, but it usually not more than 1 mole per mol of the olefincompound.

[0089] The hydroxy adduct compound of formula (IIIb):

X—(R₁)(R₂)C—C(R₃)(R₄)OH   (IIIb)

[0090] wherein X represents a hydroxy group and R1 to R4 represent thesame as defined above, can be produced, as a major product, preferablyby reacting the olefin of formula (I) with aqueous hydrogen peroxide at0 to 65° C., wherein the amount of aqueous hydrogen peroxide ispreferably 1 to 2 moles per mol of the olefin compound.

[0091] The β-hydroxyhydroperoxide compound of formula (III) wherein Xrepresents a hydroperoxide group, can be produced, as a major product,preferably in the presence of an organic solvent and a dehydrating agentat 0 to 45° C., wherein the amount of hydrogen peroxide is preferably 2to 10 moles per mol of the olefin compound.

[0092] Examples of the dehydrating agent include, for example, anhydrousmagnesium sulfate, sodium sulfate. The amount of such a dehydratingagent that may be used is not particularly limited, and preferably suchan amount of the dehydrating agent that can absorb, as crystal water,water that may be present in an aqueous hydrogen peroxide solution.

[0093] Next the olefin compound of formula (I) is described.

[0094] Examples of the olefin compound include, for example, amono-substituted olefin such as 1-hexene or a di-substituted internalolefin such as cyclohexene, the carbon-carbon double bond in the olefinis cleaved by oxidation to yield an aldehyde and a carboxylic acid.

[0095] Further examples of the olefin compound include, for example,di-substituted terminal olefins such as methylenecyclohexane and thelike, and the carbon-carbon double bond in the olefin is cleaved byoxidation to yield ketone. Yet further examples of the olefin compoundinclude, for example, tri-substituted olefins such as 2-methyl-2-penteneand the like, which is reacted to yield a ketone, an aldehyde and acarboxylic acid by oxidative cleavage of the carbon-carbon double bond.Moreover, examples of the olefin compound include tetra-substitutedolefins such as 2,3-dimethyl-2-butene or the like, which is oxidized toyield ketone.

[0096] The progress of the reaction can be checked by conventionalanalyzing means such as gas chromatography, high performance liquidchromatography, thin layer chromatography, NMR and IR.

[0097] After completion of the reaction, the desired compound can beseparated by subjecting the reaction solution as-obtained or thatresulting after decomposition of the remaining hydrogen peroxide with areducing agent such as sodium sulfite, to concentration, crystallizationor the like. Moreover, the resulting compounds can also be separated byadding, if necessary, water and/or a water-immiscible organic solvent tothe reaction mixture, then extracting and subsequently concentrating theresulting organic layer. The desired compound separated may further bepurified by such a means as distillation and/or column chromatography.

[0098] Examples of the water-immiscible organic solvent include aromatichydrocarbon solvents such as toluene and xylene, halogenated hydrocarbonsolvents such as dichloromethane, chloroform and chlorobenzene, ethersolvents such as diethyl ether, methyl tert-butyl ether andtetrahydrofuran and ester solvents such as ethyl acetate. The amount ofsuch solvents that may be used is not particularly limited.

[0099] The filtrate resulting from the separation of the desiredcompound by crystallization and the separated aqueous layer resultingfrom the extraction of the reaction solution that contain the presentcatalyst composition used in the reaction and can be reused as arecovered catalyst composition, directly or after being subjected tosome treatment such as concentration if required, in the reactionaccording to the present invention.

[0100] The carboxylic acid produced may be further decarboxylated in thereaction system, to give, for example, a carboxylic acid having one lesscarbon atoms such as the case of isophorone.

[0101] Furthermore, when optical isomers are used as the organiccompound, an optically active product can be obtained according to theposition of the asymmetric carbon.

[0102] The β-hydroxyhydroperoxide of formula (III) obtained in thepresent method can be further derivatized to carbonyl compound offormula (IV):

R₁R₂C═O, and R₃R₄C═O

[0103] wherein R₁ to R₄ independently represent a hydrogen atom or anorganic residue. The reaction process comprises decomposing a hydroxyadduct compound of formula (IIIa):

X—(R₁)(R₂)C—C(R₃)(R₄)OH   (IIIa)

[0104] wherein X is a hyroperoxide group, and R₁ to R₄ are the same asdefined above.

[0105] The decomposition reaction is conducted by contacting the hydroxyadduct compound with a catalyst selected from a metal compoundcomprising an element of Group Va, VIII, Ib, IIb, IIIb, IVb, Vb orlanthanide or by heating.

[0106] Examples of the metal compound comprising an element of Group Vainclude vanadium metal, vanadium oxide, vanadium chloride, vanadiumcarbide, ammonium vanadate, an composition obtained by reacting aqueoushydrogen peroxide with vanadium, niobium, niobium chloride, niobiumoxide, niobium ethoxide.

[0107] Examples of the metal compound comprising an element of Group VIainclude rhenium metal, rhenium carbonyl, rhenium chloride.

[0108] Examples of the metal compound comprising an element of GroupVIII include iron metal, iron carbonyl, iron chloride, ironacetylacetonate, ruthenium, ruthenium carbonyl, rutheniumacetylacetonate, ruthenium chloride, tris(triphenylphosphine)rutheniumchloride, cobalt metal, cobalt acetate, cobalt bromide, rhodium metal,rhodium acetate, rhodium carbonyl, iridium metal, iridium chloride,nickel metal, nickel acetylacetonate, palladium metal, palladiumacetate, palladium on activated carbon.

[0109] Examples of the metal compound comprising an element of Group I binclude copper metal, copper bromide, copper chloride, copper acetate.

[0110] Examples of the metal compound comprising an element of Group IIb include zinc metal, zinc chloride.

[0111] Examples of the metal compound comprising an element of GroupIIIb include boron trichloride, boron trifluoride, aluminum metal,aluminum chloride.

[0112] Examples of the metal compound comprising an element of Group IVbinclude tin metal, zinc chloride.

[0113] Examples of the metal compound comprising an element of Group Vbinclude bismuth metal, bismuth chloride, antimony metal, antimonybromide.

[0114] Examples of the metal compound comprising an element oflanthanide include dysprosium metal, dysprosium chloride.

[0115] Preferred are vanadium compound, copper compound, rutheniumcompound, palladium compound and mixtuere of them.

[0116] The amount of the catalyst for the decomposition reaction isusually 0.001 to 0.95 mole per mol of the β-hydroxyhydroperoxide. Thereaction temperature is usually −20 to 100° C.

[0117] The reaction is preferably conducted in the presence of anorganic solvent that can dissolve the peroxide. Examples of the organicsolvent include the ether solvent, alcohol solvent, alkylnitrile solventas described above.

[0118] Alternatively, a hydroxy adduct compound of formula (IIIb):

X—(R₁)(R₂)C—C(R₃)(R₄)OH   (IIIb)

[0119] wherein X is a hyroxy group and R₁ to R₄ independently representa hydrogen atom or an organic residue can be produced by a process,which comprises reacting a hydroxy adduct compound of formula (IIIa):

X—(R₁)(R₂)C—C(R₃)(R₄)OH   (IIIa)

[0120] wherein X is a hyroperoxide group, and R₁ to R₄ are the same asdefined above, with a reducing agent.

[0121] Examples of the reducing agent include an inorganic salt havingreducing activity such as sodium thiosulfate and an organic compoundhaving reducing activity such as dimethylsulfide, triphenylphosphine andthe like.

[0122] The reduction reaction is usually carried out at −10 to 100° C.in an organic solvent. Examples of the organic solvent include thosedescribed above for the decomposition reaction of the hydroxy adductcompound (III).

[0123] Typical examples of the hydroxy adduct compounds include ahydroxy adduct compound of formula (III):

X—(R₁)(R₂)C—C(R₃)(R₄)OH   (III)

[0124] wherein X is a hyroperoxide group or a hydroxy group, R₁ and R₂represent a methyl group, R₃ represents a hydrogen atom, and R₄represents a group of formula;

[0125] wherein R′ represents an alkyl, aryl, or aralkyl group; and

[0126] a hydroxy adduct compound of formula (III):

X—(R₁)(R₂)C—C(R₃)(R₄)OH   (III)

[0127] wherein X is a hyroperoxide group, R₁ represents a methyl group,R₃ represents a hydrogen atom, and R₂ and R₄ form a group of formula:

[0128] The alkyl, aralkyl or ary group represented by R′ in the abovedescribed compounds respectively means the same group as defined for R₁to R₄ above.

[0129] In the above-described reduction or decomposition reaction of theβ-hydroxyhydroperoxide, the reaction mixture or solution aftercompletion of the reaction can be treated in a similar manner toseparate the desired product.

[0130] Examples of the ketone that is obtained in such a manner includeacetone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone,acetophenone, cyclobutanone, cyclopentanone, cyclohexanone,camphenilone, norpinene, 1,3,3-trimethylindorinone,dihydro-2,3-furandione, benzophenone, 2,6-hexanedione, 2,7-octanedione,1,6-cyclodecanedione, 4-acetoxyacetophenone,2-methoxy-6-(propan-2-one)acetophenone,2-carboethoxy-3-methylcyclopentanone, 4-methyl-1,2-cyclohexanedione andthe like.

[0131] Examples of the aldehyde include formaldehyde, acetaldehyde,propionaldehyde, butylaldehyde, pentylaldehyde, hexylaldehyde,heptylaldehyde, decylaldehyde, undecanylaldehyde, benzaldehyde,5-oxohexylaldehyde, 2-methyl-5-oxohexylaldehyde,4-methyl-5-oxohexylaldehyde, 3-methyl-5-oxohexylaldehyde,2,4-dimethyl-5-oxohexylaldehyde, 3,4-dimethyl-5-oxohexylaldehyde,2,3-dimethyl-5-oxohexylaldehyde, 2,3,4-trimethyl-5-oxohexylaldehyde,6-oxoheptylaldehyde, 2-methyl-6-oxoheptylaldehyde,4-methyl-6-oxoheptylaldehyde, 2,4-dimethyl-6-oxoheptylaldehyde,2,3-dimethyl-6-oxoheptylaldehyde, 3,4-dimethyl-6-oxoheptylaldehyde,2,3,4-trimethyl-6-oxoheptylaldehyde, glutaraldehyde, adipoaldehyde,heptanedialdehyde, octanedialdehyde, 2-chloroglutaraldehyde,2-methylglutaraldehyde, 3-methylglutaraldehyde,2,3-dimethylglutaraldehyde, 2,4-dimethylglutaraldehyde,2,3,4-trimethylglutaraldehyde, 2-methyladipoaldehyde,3-methyladipoaldehyde, 2,3-dimethyladipoaldehyde,2,4-dimethyladipoaldehyde, 2,3,4-dimethyladipoaldehyde,cyclopentane-1,3-dicarboaldehyde, diphenyl-2,2′-dicarboaldehyde,1-(formylmethyl)cyclopentene-2,3,4-tricarboaldehyde,1,2-bis(formylmethyl)succinic anhydride,1,4-diformylbutane-2,3-dicarboxylic acid, (2-formylmethyl)benzaldehyde,2,2-dimethyl-3-(2-oxopropyl)cyclopropaneacetaldehyde,2,2-dimethyl-3-(3-oxobutyl)cyclopropylaldehyde,2,2-dimethyl-3-(2-oxoethyl)cyclobutaneacetaldehyde, methyl3,3-dimethyl-2-formylcyclopropanecarboxylate, ethyl3,3-dimethyl-2-formylcyclopropanecarboxylate, isopropyl3,3-dimethyl-2-formylcyclopropanecarboxylate, tert-butyl3,3-dimethyl-2-formylcyclopropanecarboxylate, cyclohexyl3,3-dimethyl-2-formylcyclopropanecarboxylate, menthyl3,3-dimethyl-2-formylcyclopropanecarboxylate, benzyl3,3-dimethyl-2-formylcyclopropanecarboxylate, (4-chlorobenzyl)3,3-dimethyl-2-formylcyclopropanecarboxylate,(2,3,5,6-tetrafluorobenzyl)3,3-dimethyl-2-formylcyclopropanecarboxylate,(2,3,5,6-tetrafluoro-4-methylbenzyl)3,3-dimethyl-2-formylcyclopropanecarboxylate,(2,3,5,6-tetrafluoro-4-methoxybenzyl)3,3-dimethyl-2-formylcyclopropanecarboxylate,(2,3,5,6-tetrafluoro-4-methoxymethylbenzyl)3,3-dimethyl-2-formylcyclopropanecarboxylate and (3-phenoxybenzyl)3,3-dimethyl-2-formylcyclopropanecarboxylate.

[0132] Examples of the carboxylic acid include acetic acid, propionicacid, butanoic acid, pentanoic acid, hexanoic acid, 6-oxoheptanoic acid,2-methyl-6-oxoheptanoic acid, 3-methyl-6-oxoheptanoic acid,4-methyl-6-oxoheptanoic acid, 5-methyl-6-oxoheptanoic acid,2,3-dimethyl-6-oxoheptanoic acid, 2,4-dimethyl-6-oxoheptanoic acid,3,4-dimethyl-6-oxoheptanoic acid, 2,3,4-trimethyl-6-oxoheptanoic acid,5-oxohexanoic acid, 2-methyl-5-oxohexanoic acid, 3-methyl-5-oxohexanoicacid, 4- methyl-5-oxohexanoic acid, 2,3-dimethyl-5-oxohexanoic acid,2,4-dimethyl-5-oxohexanoic acid, 3,4-dimethyl-5-oxohexanoic acid,2,3,4-trimethyl-5-oxohexanoic acid, 3,3-dimethyl-5-oxohexanoic acid,heptanoic acid, glutaric acid, adipic acid, pimelic acid, suberic acid,2-methylglutaric acid, 3-methylglutaric acid, 3-chloroglutaric acid,2,3-dimethylglutaric acid, 2,4-dimethylglutaric acid, 2-methyladipicacid, 3-methyladipic acid, 2,3-dimethyladipic acid, 2,4-dimethyladipicacid, 3,4-dimethyladipic acid, 2,3,4-trimethylglutaric acid,cyclopentane-1,3-dicarboxylic acid, biphenyl-2,2′-dicarboxylic acid,meso-1,2,3,4-tetracarboxylic acid, benzoic acid,1-(carboxymethyl)cyclopentane-2,3,4-tricarboxylic acid, homophthalicacid, benzyloxyacetic acid,3-(3-oxobutyl)-2,2-dimethylcyclopropanecarboxylic acid,3-(2-oxopropyl)-2,2-dimethyl-1carboxymethylcyclopropane,3-(2-oxoethyl)-2,2-dimethyl-1-carboxymethylcyclobutane, methyl3,3-dimethyl-2-carboxycyclopropanecarboxylate, ethyl3,3-dimethyl-2-carboxycyclopropanecarboxylate, isopropyl3,3-dimethyl-2-carboxycyclopropanecarboxylate, tert-butyl3,3-dimethyl-2-carboxycyclopropanecarboxylate, cyclohexyl3,3-dimethyl-2-carboxycyclopropanecarboxylate, menthyl3,3-dimethyl-2-carboxycyclopropanecarboxylate, benzyl3,3-dimethyl-2-carboxycyclopropanecarboxylate, (4-chlorobenzyl)3,3-dimethyl-2-carboxycyclopropanecarboxylate,(2,3,5,6-tetrafluorobenzyl)3,3-dimethyl-2-carboxycyclopropanecarboxylate,(2,3,5,6-tetrafluoro-4-methylbenzyl)3,3-dimethyl-2-carboxycyclopropanecarboxylate,(2,3,5,6-tetrafluoro-4-methoxybenzyl)3,3-dimethyl-2-carboxycyclopropanecarboxylate,(2,3,5,6-tetrafluoro-4-methoxymethylbenzyl)3,3-dimethyl-2-carboxycyclopropanecarboxylate, (3-phenoxybenzyl)3,3-dimethyl-2-carboxycyclopropanecarboxylate and the like.

EXAMPLES

[0133] The present invention is further described in detail below withreference to examples, but the invention is not limited to theseexamples. Gas chromatography method(hereinafter referred to as GCmethod) Column: DB-1 (Length: 30 m, i.d.: 0.25 mm, Film thickness: 1.0μm) Oven temperature: Initial temp.: 100° C. (0 min)→Rate: 2° C./min→Second temp.: 180° C. (0 min)→Rate: 10° C./min→ Final temp.: 300° C.(10min) Run time: 62 min Injection temp: 250° C., Detection temp: 250° C.Carrier gas: He, constant flow 1.0 ml/min Injection vol.: 1.0 μl, Splitratio: 1/10 Liquid chromatography method(herein after referred to as LCmethod) Column: Sumipax ODS-A212(Length: 15 cm, i.d.: 6 mm, 5.0 μm)Carrier: A 0.1 vol % trifluoroacetic acid/water B 0.1 vol %trifluoroacetic acid/acetonitrile Initial A/B = 90/10(volume ratio) (0min) → after 40 min A/B = 10/90(volume ratio) (20 min), flow: 1.0 ml/minInjection vol.: 10 μl, Detector: 220 nm,

Example 1

[0134] Two grams of a 30 wt % aqueous hydrogen peroxide solution and 97mg of metallic tungsten were charged into a 50 mL flask equipped with amagnetic rotor and a reflux condenser. The mixture was heated to aninner temperature of 60° C. and then was stirred and maintained at thetemperature for 0.5 hour. To the mixture, 3.5 g of isophorone and 25.8 gof a 30 wt % aqueous hydrogen peroxide solution were added dropwise over20 minutes. After completion of the addition, the reaction solution washeated and stirred for 6 hours on an oil bath inner temperature of whichwas 95° C. After completion of the reaction, the mixture was cooled toan inner temperature of 25° C. and was analyzed by gas chromatography.The analysis confirmed that 3,3-dimethyl-5-oxohexanoic acid (arealpercentage of chromatogram: 55%) was formed.

Example 2

[0135] Two grams of a 30 wt % aqueous hydrogen peroxide solution and 30mg of metallic tungsten were charged into a 50 mL flask equipped with amagnetic rotor and a reflux condenser. The mixture was heated to aninner temperature of 60° C. and then stirred and maintained at thetemperature for 0.5 hour. To the resulting mixture, 3.0 g of methyl

[0136] 3,3-dimethyl-2-(2-methyl-1propenyl)cyclopropanecarboxylate and7.3 g of a 30 wt % aqueous hydrogen peroxide solution were charged.After the charge, the reaction solution was heated and stirred for 6hours on an oil bath inner temperature of which was 95° C. Aftercompletion of the reaction, the mixture was cooled to an innertemperature of 25° C. and was analyzed by an internal standard method bygas chromatography. The analysis confirmed that3,3-dimethyl-2-carbomethoxycyclopropanecarboxylic acid (arealpercentage: 43%) was formed.

Example 3

[0137] Two grams of a 30 wt % aqueous hydrogen peroxide solution and 90mg of metallic tungsten were charged into a 50 mL flask equipped with amagnetic rotor and a reflux condenser. The mixture was heated to aninner temperature of 60° C. and then was stirred and maintained at thetemperature for 0.5 hour. To the mixture, 4.7 g of 1-methylcyclohexeneand 25.6 g of a 30 wt % aqueous hydrogen peroxide solution were added.The reaction solution was thereafter heated and stirred for 10 hours onan oil bath inner temperature of which was 95° C. After completion ofthe reaction, the mixture was cooled to an inner temperature of 25° C.and was analyzed by an internal standard method by gas chromatography.The analysis confirmed that 6-oxohexanoic acid (yield: 92%) was formed.

Example 4

[0138] Into a 50 mL flask equipped with a magnetic rotor and a refluxcondenser, 200 mg of a 30 wt % aqueous hydrogen peroxide solution and 40mg of tungsten boride were added. The mixture was heated to an innertemperature of 40° C. and then was stirred and maintained at thetemperature for 0.5 hour. After cooling of this solution to an innertemperature of 25° C., 530 mg of anhydrous magnesium sulfate, 530 mg ofa 30 wt % aqueous hydrogen peroxide solution and 1.5 g of tert-butanolwere added and then stirred and maintained at the temperature for 1hour. Thereafter a mixed solution comprising 350 mg of 3-carene and 1.5g of tert-butanol was added dropwise over 10 minutes. The mixture wasstirred and maintained at an inner temperature of 25° C. for 24 hours,to this solution 10 g of toluene and 5 g of water was added, andseparated to give 9.4 g of the toluene solution. Gas chromatographyanalysis (an internal standard method) and a liquid chromatographyanalysis of this reaction solution confirmed that the yield of4-hydroxy-3-hydroperoxycarene was 70.4% and the yield of 3,4-carenediol21.7%.

[0139] The liquid chromatographys' elution time of4-hydroxy-3-hydroperoxycarene is 20.9 min. and the mass spectrum showedM+186.

[0140] Into a 50 mL flask equipped with a magnetic rotor and a refluxcondenser, 200 mg of a 30 wt % aqueous hydrogen peroxide solution and 20mg of vanadium metal were charged. The mixture was stirred andmaintained at the temperature for 0.5 hour. After cooling this solutionto an inner temperature of 25° C., the toluene solution of4-hydroxy-3-hydroperoxycarene was added and then was stirred andmaintained at that temperature for 16 hour and then was heated to aninner temperature of 60° C. and then further stirred and maintained atthe temperature for 3 hour. Gas chromatography analysis (an internalstandard method) and a liquid chromatography analysis of this reactionsolution confirmed that the yield of2,2,-dimethyl-3-(2-oxopropyl)cyclopropane acetaldehyde was 71.4% (interms of used 3-carene).

Example 5

[0141] Into a 50 mL flask equipped with a magnetic rotor and a refluxcondenser, 200 mg of a 30 wt % aqueous hydrogen peroxide solution, 0.8 gof tert-butanol and 22 mg of tungsten boride were charged. The mixturewas heated to an inner temperature of 60° C. and then was stirred andmaintained at the temperature for 1 hour. After cooling this solution to25° C., 530 mg of anhydrous magnesium sulfate was added and thereafter amixed solution comprising 270 mg of 1-methylcyclohexene, 1.0 g oftert-butanol and 500 mg of a 30 wt % aqueous hydrogen peroxide solutionwas added dropwise over 20 minutes. After the addition, the mixture wasstirred and maintained at an inner temperature of 25° C. for 20 hours.Analysis of the reaction solution by gas chromatography confirmed that6-oxoheptylaldehyde (areal percentage: 77.0%) was formed.

Example 6

[0142] Into a 50 mL flask equipped with a magnetic rotor and a refluxcondenser, 3 g of tert-butanol, 600 mg of a 30 wt % aqueous hydrogenperoxide solution, 2.3 g of magnesium sulfate, 300 mg of boric anhydrideand 40 mg of tungsten boride were charged. The mixture was heated to aninner temperature of 60° C. and then was stirred and maintained at thetemperature for 1 hour. After cooling to an inner temperature of 6° C.,a mixed solution comprising 400 mg of methyltrans-3,3-dimethyl-2-(2-methyl-1-propenyl)cyclopropanecarboxylate, 600mg of a 30 wt % aqueous hydrogen peroxide solution and 1.8 g oftert-butanol was added dropwise over 20 minutes. The mixture was stirredand maintained at an inner temperature of 6° C. for 4 days, to give areaction solution containing methyltrans-3,3-dimethyl-(1-hydroxy-2-hydroperoxy-2-methylpropyl)cyclopropane-carboxylateand methyl trans-3,3-dimethyl-2-formylcyclopropanecarboxylate. Gaschromatography analysis (an internal standard method) and a liquidchromatography analysis of this reaction solution confirmed that theyield oftrans-3,3-dimethyl-(1-hydroxy-2-hydroperoxy-2-methylpropyl)cyclopropane-carboxylatewas 55% and the yield of methyltrans-3,3-dimethyl-2-formylcyclopropanecarboxylate was 5%.

Example 7

[0143] Into a 50 mL flask equipped with a magnetic rotor and a refluxcondenser, 200 mg of a 30 wt % aqueous hydrogen peroxide solution and 45mg of tungsten boride were charged. The mixture was heated to an innertemperature of 40° C. and then was stirred and maintained at thattemperature for 1 hour. After cooling this solution to an innertemperature of 20° C., 530 m g of anhydrous magnesium sulfate, 400 mg ofa 30 wt % aqueous hydrogen peroxide solution and 1.5 g of tert-butanolwas added and then stirred and maintained at the temperature for 2 hour.Thereafter a mixed solution comprising 400 mg of methyltrans-3,3-dimethyl-2-(2-methyl-1-propenyl)cyclopropanecarboxylate, and0.8 g of tert-butanol was added dropwise over 20 minutes. The mixturewas stirred and maintained at an inner temperature of 25° C. for 16hours, to give a reaction solution containing methyltrans-3,3-dimethyl-(1-hydroxy-2-hydroperoxy-2-methylpropyl)cyclopropane-carboxylateand methyl trans-3,3-dimethyl-2-formylcyclopropanecarboxylate. Gaschromatography analysis (an internal standard method) and a liquidchromatography analysis of this reaction solution confirmed that theyield oftrans-3,3-dimethyl-(1-hydroxy-2-hydroperoxy-2-methylpropyl)cyclopropane-carboxylatewas 60.8% and the yield of methyltrans-3,3-dimethyl-2-formylcyclopropanecarboxylate was 6% .

Example 8

[0144] Into a 50 mL flask, 3 g of tert-butanol, 200 mg of a 30 wt %aqueous hydrogen peroxide solution, 16 mg of boric anhydride and 40 mgof metallic tungsten (powder) were charged. The mixture was heated to aninner temperature of 60° C. and then was stirred and maintained at thetemperature for 1 hour. After the cooling this solution to an innertemperature of 25° C., 530 mg of magnesium sulfate was added andthereafter a mixed solution comprising 400 mg of methyltrans-3,3-dimethyl-2-(2-methyl-1-propenyl)cyclopropane-carboxylate, 600mg of a 30 wt % aqueous hydrogen peroxide solution and 1.8 g oftert-butanol was added dropwise over 20 minutes. The mixture was stirredand maintained at an inner temperature of 25° C. for 16 hours, to give areaction solution containing methyltrans-3,3-dimethyl-(1-hydroxy-2-hydroperoxy-2-methylpropyl)-cyclopropanecarboxylateand methyl trans-3,3-dimethyl-2-formylcyclopropanecarboxylate. Gaschromatography analysis (an internal standard method) and liquidchromatography analysis of this reaction solution confirmed that theyield oftrans-3,3-dimethyl-(1-hydroxy-2-hydroperoxy-2-methylpropyl)cyclopropane-carboxylatewas 54.8% and the yield of methyltrans-3,3-dimethyl-2-formylcyclopropanecarboxylate was 6%

Example 9

[0145] Into a 100 mL flask, 10 g of tert-butanol, 2.0 g of a 30 wt %aqueous hydrogen peroxide solution and 215 mg of tungsten boride werecharged. The mixture was heated to an inner temperature of 60° C. andthen was stirred and maintained at that temperature for 1 hour. Aftercooling to an inner temperature of 20° C., a mixed solution comprising 4g of methyltrans-3,3-dimethyl-2-(2-methyl-1-propenyl)cyclopropanecarboxylate, 4 gof a 30 wt % aqueous hydrogen peroxide solution and 10 g of tert-butanolwas dropped over 20 minutes. The mixture was stirred and maintained atan inner temperature of 20° C. for 48 hours, to give a reaction solutioncontaining methyltrans-3,3-dimethyl-(1-hydroxy-2-hydroperoxy-2-methylpropyl)cyclopropane-carboxylateand methyl trans-3,3-dimethyl-2-formylcyclopropanecarboxylate. Gaschromatography analysis (an internal standard method) and a liquidchromatography analysis of this reaction solution confirmed that theyield oftrans-3,3-dimethyl-(1-hydroxy-2-hydroperoxy-2-methylpropyl)cyclopropane-carboxylatewas 36% and the yield of methyltrans-3,3-dimethyl-2-formylcyclopropanecarboxylate was 4%

Example 10

[0146] Into a 50 mL flask, 3 g of tert-butanol, 200 mg of a 30 wt %aqueous hydrogen peroxide solution and 40 mg of metallic tungsten(powder) were charged. The mixture was heated to an inner temperature of60° C. and then was stirred and maintained at th temperature for 1 hour.After cooling to an inner temperature of 25° C., a mixed solutioncomprising 400 mg of methyltrans-3,3-dimethyl-2-(2-methyl-1-propenyl)cyclopropanecarboxylate, 400mg of a 30 wt % aqueous hydrogen peroxide solution and 1.8 g oftert-butanol was added dropwise over 20 minutes. The mixture was stirredand maintained at an inner temperature of 25° C. for 24 hours, to give areaction solution containing methyltrans-3,3-dimethyl-(1-hydroxy-2-hydroperoxy-2-methylpropyl)cyclopropane-carboxylateand methyl trans-3,3-dimethyl-2-formylcyclopropanecarboxylate. Gaschromatography analysis (an internal standard method) and a liquidchromatography analysis of this reaction solution confirmed that theyield oftrans-3,3-dimethyl-(1-hydroxy-2-hydroperoxy-2-methylpropyl)cyclopropanecarboxylate was 45% and the yield of methyltrans-3,3-dimethyl-2-formylcyclopropanecarboxylate was 5%

Example 11

[0147] Into a 50 mL flask, 3 g of methyl tert-butyl ether, 1.2 g of a 30wt % aqueous hydrogen peroxide solution and 40 mg of tungsten boridewere charged. The mixture was heated to an inner temperature of 50° C.and then was stirred and maintained at the temperature for 1 hour.Subsequently, 2.3 g of magnesium sulfate was added and thereafter amixed solution comprising 400 mg of methyltrans-3,3-dimethyl-2-(2-methyl-1propenyl)cyclopropanecarboxylate and 1.8g of methyl tert-butyl ether was added dropwise over 20 minutes. Themixture was stirred and maintained at an inner temperature of 50° C. for2 hours, to give a reaction solution containing methyltrans-3,3-dimethyl-(1-hydroxy-2-hydroperoxy-2-methylpropyl)cyclopropane-carboxylateand methyl trans-3,3-dimethyl-2-formylcyclopropanecarboxylate. Gaschromatography analysis (an internal standard method) and a liquidchromatography analysis of this reaction solution confirmed that theyield oftrans-3,3-dimethyl-(1-hydroxy-2-hydroperoxy-2-methylpropyl)cyclopropane-carboxylatewas 37% and the yield of methyltrans-3,3-dimethyl-2-formylcyclopropanecarboxylate was 4%

Example 12

[0148] Into a 50 mL flask, 3 g of tert-butanol, 2.3 g of magnesiumsulfate, 300 mg of boric anhydride and 40 mg of tungsten boride werecharged. After heating to an inner temperature of 60° C., a mixedsolution comprising 400 mg of methyltrans-3,3-dimethyl-2-(2-methyl-1-propenyl)cyclopropanecarboxylate, 600mg of a 30 wt % aqueous hydrogen peroxide solution and 1.8 g oftert-butanol was added dropwise over 20 minutes and the resultingmixture was stirred and maintained at an inner temperature of 60° C. for2 hours, to give a reaction solution containing methyltrans-3,3-dimethyl-(1-hydroxy-2-hydroperoxy-2-methylpropyl)cyclopropane-carboxylateand methyl trans-3,3-dimethyl-2-formylcyclopropanecarboxylate. Gaschromatography analysis (an internal standard method) and a liquidchromatography analysis of this reaction solution confirmed that theyield oftrans-3,3dimethyl-(1-hydroxy-2-hydroperoxy-2-methylpropyl)cyclopropane-carboxylatewas 42.2% and the yield of methyltrans-3,3-dimethyl-2-formylcyclopropanecarboxylate was 5%

Example 13

[0149] Into a 50 mL flask, 3 g of tert-butanol and 51 mg of tungstensulfide were charged. After heating to an inner temperature of 60° C., amixed solution comprising 400 mg of methyltrans-3,3-dimethyl-2-(2-methyl-1-propenyl)cyclopropanecarboxylate, 1.5 gof a 30 wt % aqueous hydrogen peroxide solution and 1.8 g oftert-butanol was dropped over 20 minutes and the resulting mixture wasstirred and maintained at an inner temperature of 60° C. for 2 hours, togive a reaction solution containing methyltrans-3,3-dimethyl-2-formylcyclopropanecarboxylate. Gas chromatographyanalysis of this reaction solution confirmed that the areal percentageof methyl trans-3,3-dimethyl-2-formylcyclopropanecarboxylate was 23.8%.

Example 14

[0150] A reaction solution containing methyltrans-3,3-dimethyl-2-formylcyclopropanecarboxylate was obtained throughoperations conducted as in Example 13 except that 50 mg of tungstensilicide was used in place of 51 mg of tungsten sulfide. Gaschromatography analysis of this reaction solution confirmed that theareal percentage of methyltrans-3,3-dimethyl-2-formylcyclopropanecarboxylate was 29.8%.

Example 15

[0151] A reaction solution containing methyltrans-3,3-dimethyl-2-formylcyclopropanecarboxylate was obtained throughoperations conducted in the same manner as Example 13 except that 41 mgof tungsten carbide was used in place of 51 mg of tungsten sulfide. Gaschromatography analysis of this reaction solution confirmed that theareal percentage of methyltrans-3,3-dimethyl-2-formylcyclopropanecarboxylate was 27.7%.

Example 16

[0152] Into a 50 mL flask 20 mg of metallic molybdenum (powder) wascharged and then 200 mg of a 30 wt % aqueous hydrogen peroxide solutionwas added, followed by the addition of 530 mg of magnesium sulfate.Furthermore, a mixed solution comprising 400 mg of methyltrans-3,3-dimethyl-2-(2-methyl-1-propenyl)cyclopropanecarboxylate, 600mg of a 30 wt % aqueous hydrogen peroxide solution and 1.5 g oftert-butanol was added dropwise over 20 minutes and the resultingmixture was stirred and maintained at an inner temperature of 25° C. for40 hours, to give a reaction solution containing methyltrans-3,3-dimethyl-(1-hydroxy-2-hydroperoxy-2-methylpropyl)cyclopropane-carboxylateand methyl trans-3,3-dimethyl-2-formylcyclopropanecarboxylate. Gaschromatography analysis (an internal standard method) and a liquidchromatography analysis of this reaction solution confirmed that theyield oftrans-3,3-dimethyl-(1-hydroxy-2-hydroperoxy-2-methylpropyl)cyclopropane-carboxylatewas 51.7% and the yield of methyltrans-3,3-dimethyl-2-formylcyclopropanecarboxylate was 5%. The analysisalso revealed that 18.2% (GC areal percentage) of the starting methyltrans-3,3-dimethyl-2-(2-methyl-1-propenyl)cyclopropanecarboxylateremained.

Example 17

[0153] A reaction solution containing methyltrans-3,3-dimethyl-2-formylcyclopropanecarboxylate was obtained in asimilar manner as in Example 16 except that the amount of the metallicmolybdenum (powder) and the reaction time were changed to 40 mg and 20hours, respectively. Gas chromatography analysis (an internal standardmethod) of this reaction solution confirmed that the yield was 62.7%.The analysis also revealed that 6% (GC areal percentage) of the startingmethyl trans-3,3-dimethyl-2-(2-methyl-1-propenyl)cyclopropanecarboxylateremained.

Example 18

[0154] A reaction solution containing methyltrans-3,3-dimethyl-2-formylcyclopropanecarboxylate was obtained in asimilar manner as in Example 16 except that 22 mg of molybdenum boridewas used in place of 20 mg of metallic molybdenum. Gas chromatographyanalysis (an internal standard method) and a liquid chromatographyanalysis of this reaction solution confirmed that the yield oftrans-3,3-dimethyl-(1-hydroxy-2-hydroperoxy-2-methylpropyl)cyclopropane-carboxylatewas 36.5% and the yield of methyltrans-3,3-dimethyl-2-formylcyclopropanecarboxylate was 4% The analysisalso revealed that 20% (GC areal percentage) of the starting methyltrans-3,3-dimethyl-2-(2-methyl-1-propenyl)cyclopropanecarboxylateremained.

Example 19

[0155] A reaction solution containing methyltrans-3,3-dimethyl-2-formylcyclopropanecarboxylate was obtained in asimilar manner as in Example 16 except that methyl tert-butyl ether wasused in place of tert-butanol. Gas chromatography analysis (an internalstandard method) and a liquid chromatography analysis of this reactionsolution confirmed that the yield oftrans-3,3-dimethyl-(1-hydroxy-2-hydroperoxy-2-methylpropyl)cyclopropane-carboxylatewas 47.2% and the yield of methyltrans-3,3-dimethyl-2-formylcyclopropanecarboxylate was 5% The analysisalso revealed that 20% (GC areal percentage) of the starting methyltrans-3,3-dimethyl-2-(2-methyl-1-propenyl)cyclopropanecarboxylateremained.

Example 20

[0156] Twenty grams of a 30 wt % aqueous hydrogen peroxide solution and895 mg of metallic tungsten powder were charged into a 1 L flaskequipped with an induction stirrer and a reflux condenser and the innertemperature was elevated to 60° C. After heating and maintaining of themixture at the temperature for 0.5 hour, 40 g of cyclohexene and 228 gof a 30 wt % aqueous hydrogen peroxide solution were added dropwise over20 minutes. After completion of the dropping, the reaction solution washeated and stirred for 8 hours on an oil bath inner temperature of whichwas 100° C. The inner temperature of the reaction solution was elevatedfrom 72° C. to 95° C. After completion of the reaction, the mixture wascooled to an inner temperature of 5° C., and the crystals formed wereseparated by filtration and dried, to give 57.3 g of white crystals. Theanalysis of the crystals with 1H-NMR confirmed that they were adipicacid of high purity. The measurement of the melting point of thecrystals confirmed the melting point was 151 to 152° C. The analysis ofthe filtrate by gas chromatography (the internal standard method) showedthat the filtrate contained 9.6 g of adipic acid. The total yield ofadipic acid resulting from the separated crystals of adipic acid and theadipic acid in the filtrate was 94%.

Example 21

[0157] The filtrate obtained in Example 20 was concentrated to 188 g.The concentrated filtrate was charged into a 1 L flask equipped with aninduction stirrer and a reflux condenser, and 40 g of cyclohexene and250 g of a 30 wt % aqueous hydrogen peroxide solution were addeddropwise over 20 minutes. After the dropping, the mixture was heated andstirred for 9 hours on an oil bath inner temperature of which was 100°C. The inner temperature of the reaction solution was elevated from 72°C. to 95° C. After completion of the reaction, the mixture was cooled toan inner temperature of 0° C., and the crystals formed were separated byfiltration and dried, to give 57.2 g of white crystals of adipic acid.Melting point: 151 to 152° C. The filtrate was concentrated to 130 g andcooled to an inner temperature of 0° C. The crystals formed wereseparated by filtration and dried, to give 5.0 g of white crystals ofadipic acid. Melting point: 151 to 152° C. The yield of the crystals ofadipic acid obtained was 87.5%.

Example 22

[0158] Into a 1 L flask equipped with an induction stirrer and a refluxcondenser, 122 g of the filtrate obtained in Example 21 was charged, andthen 40 g of cyclohexene and 250 g of a 30 wt % aqueous hydrogenperoxide solution were further dropped over 20 minutes. After theaddition, the mixture was heated and stirred for 11.5 hours on an oilbath inner temperature of which was 100° C. The inner temperature of thereaction solution was elevated from 72° C to 95° C. After completion ofthe reaction, the mixture was cooled to an inner temperature of 0° C.,and the crystals formed were separated by filtration and dried, to give57.5 g of white crystals of adipic acid. Melting point: 151 to 152° C.The filtrate was concentrated to 128 g and cooled to an innertemperature of 0° C. The crystals formed were further separated byfiltration and dried, to give 5.2 g of white crystals of adipic acid.Melting point: 151 to 152° C. The yield of the crystals of adipic acidobtained was 88.2%.

Example 23

[0159] Into a 1 L flask equipped with an induction stirrer and a refluxcondenser, 103 g of the filtrate obtained in Example 22 was charged, andthen 40 g of cyclohexene and 250 g of a 30 wt % aqueous hydrogenperoxide solution were further added dropwise over 20 minutes. After theaddition, the mixture was heated and stirred for 10.5 hours on an oilbath inner temperature of which was 100° C. The inner temperature of thereaction solution was elevated from 72° C. to 95° C. After completion ofthe reaction, the mixture was cooled to an inner temperature of 0° C.,and the crystals formed were separated by filtration and dried, to give55.7 g of white crystals of adipic acid. Melting point: 151 to 152° C.The analysis of the filtrate by gas chromatography (internal standardmethod) showed that the filtrate contained 11.6 g of adipic acid. Theyield of adipic acid was 88.9% except the adipic acid contained in 103 gof the filtrate obtained in Example 22.

Example 24

[0160] Into a 50 mL flask equipped with a magnetic rotor and a refluxcondenser, 2 g of a 30 wt % aqueous hydrogen peroxide solution and 97 mgof metallic tungsten powder were charged and heated to an innertemperature of 60° C. After the heating and maintaining of the mixtureat the temperature for 0.5 hour, 4 g of cyclohexene and 25.8 g of a 30wt % aqueous hydrogen peroxide solution were added dropwise over 20minutes. After the addition, the mixture was heated and stirred for 6hours on an oil bath inner temperature of which was 100° C. The innertemperature of the reaction solution was elevated from 72° C. to 95° C.After completion of the reaction, the mixture was cooled to an innertemperature of 5° C., and the crystals formed were separated byfiltration and dried, to give 5.3 g of white crystals. The analysis ofthe crystals with 1H-NMR confirmed that they were adipic acid of highpurity. The analysis of the filtrate by gas chromatography (an internalstandard method) showed that the filtrate contained 1.4 g of adipicacid. The total yield of adipic acid was 94%.

Example 25

[0161] Through the operations conducted in a similar manner as those inExample 24 except that 96 mg of tungsten carbide was used in place of 97mg of the metallic tungsten powder, 4.5 g of crystals of adipic acidwere obtained. The filtrate contained 1.2 g of adipic acid. The totalyield of adipic acid was 80%.

Example 26

[0162] Through the operations conducted in a similar manner as those inExample 24 except that 96 mg of tungsten boride was used in place of 97mg of the metallic tungsten powder, 3.6 g of crystals of adipic acidwere obtained. The yield of adipic acid: 51%.

Example 27

[0163] Through the operations conducted in a similar manner as those inExample 24 except that 121 mg of tungsten sulfide was used in place of97 mg of the metallic tungsten powder, 5.0 g of crystals of adipic acidwere obtained. The filtrate contained 1.12 g of adipic acid. The totalyield of adipic acid: 86%.

Example 28

[0164] Through the operations conducted in a similar manner as those inExample 24 except that 3.2 g of cyclopentene was used in place of 4 g ofcyclohexene, 4.2 g of crystals of glutaric acid were obtained. Thefiltrate contained 0.93 g of glutaric acid. The total yield of adipicacid resulting from the combination of the separated crystals ofglutaric acid and the glutaric acid in the filtrate was 80%.

Example 29

[0165] Into a 50 mL flask equipped with a magnetic rotor and a refluxcondenser, 0.5 g of a 30 wt % aqueous hydrogen peroxide solution and 37mg of metallic tungsten were charged. The mixture was heated to an innertemperature of 60° C. and then was stirred and maintained at thetemperature for 0.5 hour. To the mixture were charged 2.0 g of 1-hepteneand 7.5 g of a 50 wt % aqueous hydrogen peroxide solution. After that,the reaction solution was heated and stirred for 20 hours on an oil baththe inner temperature of which was 95° C. After completion of thereaction, the reaction solution was cooled to an inner temperature of25° C. and analyzed by gas chromatography (an internal standard method).The analysis showed that 1.2 g of hexanoic acid was formed. Yield: 49%.

Example 30

[0166] Into a 50 mL flask equipped with a magnetic rotor and a refluxcondenser, 2 g of a 30 wt % aqueous hydrogen peroxide solution and 70 mgof metallic tungsten were charged. The mixture was heated to an innertemperature of 60° C. and then stirred and maintained at thattemperature for 0.5 hour. To the mixture were charged 4 g of styrene and15 g of a 40 wt % aqueous hydrogen peroxide solution. The mixture washeated and stirred for 30 hours on an oil bath the inner temperature ofwhich was 95° C. After completion of the reaction, the reaction solutionwas cooled to an inner temperature of 25° C., to give 4.3 g of whitecrystals of benzoic acid. An analysis by gas chromatography confirmedthat the purity of the crystals obtained was 98% (areal percentage).

Example 31

[0167] Into a 50 mL flask equipped with a magnetic rotor and a refluxcondenser, 200 mg of a 30 wt % aqueous hydrogen peroxide solution, 1.5 gof tert-butanol and 40 mg of metallic tungsten powder were charged. Themixture was heated to an inner temperature of 60° C. and then wasstirred and maintained at the temperature for 1 hour. After cooling ofthis solution to an inner temperature of 25° C., 530 mg of anhydrousmagnesium sulfate was added and then a mixed solution comprising 150 mgof cyclopentene, 1.5 g of tert-butanol and 350 mg of a 30 wt % aqueoushydrogen peroxide solution was added dropwise over 20 minutes. Afterstirring and maintaining the mixture at an inner temperature of 25° C.for 16 hours, gas chromatography analysis (an internal standard method)and a liquid chromatography analysis of this reaction solution confirmedthat the yield of 1-hydroxy-2-hydroperoxy-cyclopentane was 80.7%. Almostno by-production of the diol compound was recognized.

Example 32

[0168] Into a 50 mL flask equipped with a magnetic rotor and a refluxcondenser, 200 mg of a 30 wt % aqueous hydrogen peroxide solution, 1.5 gof tert-butanol, 20 mg of boric anhydride and 40 mg of metallic tungstenpowder were charged. The mixture was heated to an inner temperature of60° C. and then was stirred and maintained at that temperature for 1hour. After cooling of this solution to an inner temperature of 25° C.,530 mg of anhydrous magnesium sulfate was added and then a mixedsolution comprising 180 mg of cyclohexene, 1.5 g of tert-butanol and 350mg of a 30 wt % aqueous hydrogen peroxide solution was added dropwiseover 20 minutes. After stirring and maintaining the mixture at an innertemperature of 25° C. for 16 hours, gas chromatography analysis (aninternal standard method) and a liquid chromatography analysis of thisreaction solution confirmed that the yield of1-hydroxy-2-hydroperoxy-cyclohexane was 54.7%.

Example 33

[0169] Through the operations conducted in a similar manner as those inExample 32 except that 220 mg of 1-heptene was used in place of 180 mgof cyclohexene and that the mixture was stirred and maintained at aninner temperature of 25° C. for 48 hours, 55 mg of hexylaldehyde wasobtained. Yield: 25%.

Example 34

[0170] Through the operations conducted in a similar manner as those inExample 32 except that 230 mg of styrene was used in place of 180 mg ofcyclohexene and that the mixture was stirred and maintained at an innertemperature of 60° C. for 6 hours, 47 mg of benzaldehyde was obtained.Yield: 20%.

Example 35

[0171] Through the operations conducted in a similar manner as those inExample 32 except that 370 mg of 5-dodecene was used in place of 180 mgof cyclohexene, that 22 mg of tungsten boride was used in place of 40 mgof metallic tungsten powder and that the mixture was stirred andmaintained at an inner temperature of 25° C. for 39 hours, 112 mg ofheptylaldehyde (yield: 44%) and pentylaldehyde (yield: 44%) wereobtained.

Example 36

[0172] Into a 50 mL flask equipped with a magnetic rotor and a refluxcondenser, 200 mg of a 30 wt % aqueous hydrogen peroxide solution, 40 mgof metallic tungsten powder and 15 mg of boric anhydride and werecharged and the mixture was heated to an inner temperature of 60° C.After stirring and maintaining at the temperature for 0.5 hour, themixture was cooled to an inner temperature of 25° C. After addition of1.5 g of tert-butanol and 530 mg of anhydrous magnesium sulfate, a mixedsolution comprising 230 mg of 2,3-dimethyl-2-butene, 1.5 g oftert-butanol and 350 mg of a 30 wt % aqueous hydrogen peroxide solutionwas added dropwise over 20 minutes. After completion of the addition,the mixture was stirred and maintained at an inner temperature of 25° C.for 20 hours. Analysis of the reaction solution by gas chromatographyconfirmed formation of 243 mg of acetone. The yield was 77% of thetheoretical value.

Example 37

[0173] Into a 50 mL flask equipped with a magnetic rotor and a refluxcondenser, 200 mg of a 30 wt % aqueous hydrogen peroxide solution, 1.5 gof tert-butanol, 16 mg of boric anhydride and 40 mg of metallic tungstenpowder were charged and the mixture was heated to an inner temperatureof 60° C. After stirring and maintaining at the temperature for 1 hour,530 mg of anhydrous magnesium sulfate was added and thereafter a mixedsolution containing 247 mg of 2,4,4-trimethyl-1-pentene, 1.5 g oftert-butanol and 350 mg of a 30 wt % aqueous hydrogen peroxide solutionwas added dropwise over 20 minutes. After the addition, the mixture wasstirred and maintained at an inner temperature of 60° C. for 6 hours.Analysis of the reaction solution by gas chromatography confirmed theformation of 4,4-dimethylpentane-2-one (areal percentage in the gaschromatogram: 51.0%). The by-production of an epoxy compound was alsorecognized (areal percentage in the gas chromatography analysis: 25.0%).

Example 38

[0174] To a 100 mL flask equipped with magnetic rotor and a refluxcondenser were added 4.2 g of metallic tungsten boride powder, 25 g ofwater, andl 8 grams of a 60 wt % aqueous hydrogen peroxide solution wereadded thereto under stirring at 40° C. over 2 hours. The mixture waskept at 40° C. for 2 hours to yield a clear solution with a slight whitecrystals floating on the surface of the solution. After the solution wascooled to room temperature and hydrogen peroxide was decomposed withplatinum net, the solution was evaporated to remove water at roomtemperature to give white crystals, which was dried at room temperatureunder open air until the weight thereof became constant. 6.4 g of solidcrystal was finally obtained.

[0175] UV Absorbtion of the solution (before concentration) λ^(H) ^(₂)^(O)max: 200, 235(s) nm. IR v_(max) (solution before concentration)(4000˜750 cm⁻¹): 3350, 2836, 1275, 1158, 965, 836 cm⁻¹ IR v_(max) (KBr)(Solid crystal): 3527, 3220, 2360, 2261, 1622, 1469, 1196, 973, 904.5,884, 791, 640, 549 cm⁻¹ Elemental Analysis (found): W: 51.2, O: 39.0, H:2.2, B: 3.98

Example 39

[0176] A pale yellow clear solution was obtained in a similar manner asdescribed in Example 38 except that 12 g of water was used and 5.4 g oftungsten sulfide was used in place of tungsten boride. A 10.1 g of apale yellow solid was obtained after drying.

[0177] UV Absorbtion of the solution before concentration: λ^(H) ^(₂)^(O) max 200, 240 (s) nm IR (aqueous solution before concentration) v_(max) (aqueous solution) (4000˜750 cm⁻¹): 3373, 1187, 1044, 974, 878,837 cm⁻¹ IR (Solid), v_(max) (KBr): 3435, 3359, 1730, 1632, 1320, 1285,1178, 1103, 1070, 1008, 981, 887, 839, 851, 660, 615, 578 cm⁻¹ ElementalAnalysis(found): W: 35.3, O: 47.4, H:3.0, S:12.4.

[0178] A yellowish solution was obtained in a similar manner asdescribed in Example 38 except that 12 g of water was used and 2.3 g ofmolybdenum boride was used in place of tungsten boride and 12 g of 60%hydrogen peroxide was used.

[0179] UV Absorbtion of the solution before concentration: λ^(H) ^(₂)^(O) _(max): 200, 310 (s) nm IR (Solid), v_(max) (KBr): 3221, 2520,2361, 2262, 1620, 1463, 1439, 1195, 965, 927, 887, 840, 799, 674, 634,547, 529 cm⁻¹ Elemental Analysis (found): Mo: 35.5, O: 51.0, H: 2.9, B:4.1

Example 40

[0180] To a 50 mL flask equipped with magnetic rotor and a refluxcondenser were added 80 mg of metallic tungsten powder, and 400 mg of a30 wt % aqueous hydrogen peroxide solution were added and reacted understirring for 0.5 hour. The mixture was cooled to 25° C., and 2 g oft-butanol and 800 mg of 30wt % hydrogen peroxide were added thereto andstirred for 1 hour. To this solution was added dropwise a mixed solutionof 2.0 g of t-butanol and 600 mg of 3-carene over 10 minutes and reactedfor 24 hours under stirring at 25° C. The resulting solution wassubjected to a reduction reaction by using 27 g of 5 wt % of sodiumthiosulfate and analyzed by GC to find that 3,4-carene-diol was producedin 70.0% yield.

Example 41

[0181] Into a 500 mL flask equipped with a magnetic rotor and a refluxcondenser and charged with 1. g of tungsten metal powder and 7.5 g ofwater were added dropwise 7.5 g of a 60 wt % aqueous hydrogen peroxidesolution at 60° C. over 1 hour under stirring. The resulting reactionmixture was reacted under stirring at the same temperature for 1 hour togive a clear solution. The solution was cooled to room temperature and38 g of t-butanol and 13.3 g of anhydrous magnesium sulfate were addedthereto and stirred for 14 hours at room temperature. To the obtainedslurry solution was dropwise added a mixed solution of 10 g of methyltrans-3,3-dimethyl-2-(2-methyl-1-propenyl)cyclopropanecarboxylate and 12g t-butanol over 20 minutes and reacted at 25° C. for 24 hours. 60 g ofwater was added to the reaction mixture and extracted twice with 50 g oftoluene to give 137.4 g of toluene solution.

[0182] The toluene solution was analyzed by LC to show that methyltrans-3,3-dimethyl-2-(1-hydrpoxy-2-hydroperoxy-2-methylpropyl)cyclopropane-carboxylateand methyl trans-3,3-dimethyl-2-formylcyclopropanecarboxylate wereproduced.

[0183] Methyltrans-3,3-dimethyl-2-(1-hydrpoxy-2-hydroperoxy-2-methylpropyl)-cyclopropanecarboxylate:LC Retention time: 17.8 min., LC-MS : M⁺=232.

[0184]¹H-NMR spectrum: δ 8.82 ppm, bs(—OOH).

[0185] GC and LC analysis (internal standard method) showed that theyield of methyltrans-3,3-dimethyl-2-(1-hydrpoxy-2-hydroperoxy-2-methylpropyl)cyclopropane-carboxylatewas 52,6% and that of methyltrans-3,3-dimethyl-2-formylcyclopropanecarboxylate was 5%.

[0186] The toluene solution (167 g) was subjected to a decompositionreaction as below.

[0187] Into a 500 mL flask equipped with a magnetic rotor and a refluxcondenser were charged 500 mg of vanadium pentoxide and 100 g oftoluene, and the toluene solution obtained above was dropwise addedthereto at 60° C. over 2 hours and kept at the temperature for 1 hour.The obtained solution was were analyzed by LC to show that disappearanceof the peak of methyltrans-3,3-dimethyl-2-(1-hydrpoxy-2-hydroperoxy-2-methylpropyl)cyclopropane-carboxylatein chromatogram and a peak of methyltrans-3,3-dimethyl-2-formylcyclopropanecarboxylate was detected. Yieldof methyl trans-3,3-dimethyl-2-formylcyclopropanecarboxylate was 54.5%.

Example 42

[0188] Into a 100 mL flask equipped with a magnetic rotor and a refluxcondenser were charged 400 mg of tungsten metal powder and 3 g of water,and 3 g of a 60 wt % aqueous hydrogen peroxide were added thereto at 40°C., over 1 hour under stirring, and reacted for 1 hour at the sametemperature under stirring to produce a clear homogeneous solution. Thesolution was cooled to room temperature and 15 g of t-butanol and 5.3 gof anhydrous magnesium sulfate were added thereto and stirred for 1 hourat room temperature. To the obtained slurry solution was dropwise addeda mixed solution of 4 g of methyltrans-3,3-dimethyl-2-(2-methyl-1-propenyl)cyclopropanecarboxylate and 8g t-butanol over 20 minutes and reacted at 25° C. for 24 hours. A 50 gof 5 wt % aqueous sodium thiosulfate solution was added to the reactionmixture and stirred for 24 hours at room temperature. Then the mixturewas extracted twice with 20 g of toluene to give 83.7 g of a toluenesolution. The toluene solution was analyzed by GC to show that thetoluene solution contains methyltrans-3,3-dimethyl-2-(1,2-dihydrpoxy-2-methylpropyl)cyclopropanecarboxylate,the yield of which was 80.0% (internal standard method).

[0189] The basic foreign Applications filed on Aug. 11, 2000,No.2000-244277,

[0190] filed on Oct. 27, 2000, No.2000-328816,

[0191] filed on Oct. 27, 2000, No.2000-328812,

[0192] filed on Nov. 6, 2000, No.2000-337152,

[0193] filed on Nov. 6, 2000, No.2000-337151, and

[0194] filed on Nov. 6, 2000, No.2000-337150 in Japan are herebyincorporated by reference.

What is claimed is:
 1. An oxidation catalyst composition obtained byreacting aqueous hydrogen peroxide with at least one member selectedfrom (a) a tungsten or molybdenum metal compound comprising (ia)tungsten or (ib) molybdenum and (ii) an element of Group IIIb, IVb, Vbor VIb excluding oxygen, provided that said tungsten metal compound isnot tungstencarbide.
 2. An oxidation catalyst composition obtained byreacting aqueous hydrogen peroxide with at least one member selectedfrom (a) tungsten, (b) molybdenum, or (c) a tungsten or molybdenum metalcompound comprising (ia) tungsten or (ib) molybdenum, and (ii) anelement of Group IIIb, IVb, Vb or VIb excluding oxygen, and containingan organic solvent.
 3. The oxidation catalyst according to claim 1 or 2,wherein the metal compound is tungsten boride, tungsten disulfide ormolybdenum boride.
 4. The oxidation catalyst according to claim 2,wherein the organic solvent is t-butanol or methyl t-butyl ether.
 5. Theoxidation catalyst according to claim 4, which is dehydrated.
 6. Theoxidation catalyst according to claim 5, wherein dehydrating isconducted by using anhydrous magnesium sulfate.